CN103332774B - A kind of method processing high concentration hard-degraded organic waste water - Google Patents

A kind of method processing high concentration hard-degraded organic waste water Download PDF

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Publication number
CN103332774B
CN103332774B CN201310287290.8A CN201310287290A CN103332774B CN 103332774 B CN103332774 B CN 103332774B CN 201310287290 A CN201310287290 A CN 201310287290A CN 103332774 B CN103332774 B CN 103332774B
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hydrogen peroxide
waste water
temperature
reaction
ratio
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CN103332774A (en
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刘咏
张跃春
唐一鸣
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Sichuan Normal University
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Sichuan Normal University
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Abstract

The treatment process of the high concentration hard-degraded organic waste water of introduction of the present invention is in a kettle., add waste water, first regulate the pH of waste water, add divalent iron salt again and carbon material is catalyzer, add hydrogen peroxide as oxidant, reactor is sealed, certain hour is reacted after with vigorous stirring system temperature being progressively warming up to design temperature, water outlet pH value alkali is adjusted to neutrality, the pH value of reaction system is 2.5 ~ 3.5, hydrogen peroxide dosage is 1:20 ~ 1:2 with the ratio of raw wastewater COD, the ratio of carbon material and hydrogen peroxide dosage is 1:200 ~ 1:40, the ratio of divalent iron salt and hydrogen peroxide dosage is 1:2000 ~ 1:20, stirring velocity is 100 ~ 150r/min, the top temperature heated that progressively heats up is 160 ~ 240 DEG C, reaction times is 0.5 ~ 3h.The inventive method is simple, and easy to operate, oxygenant consumption is few, and COD clearance can reach more than 85%, TOC clearance can reach more than 80%.

Description

A kind of method processing high concentration hard-degraded organic waste water
Technical field
The present invention relates to a kind for the treatment of process of high concentration hard-degraded organic waste water, belong to technical field of waste water processing.
Background technology
Along with the fast development of the industry such as oil, chemical industry and pharmacy, create the organic industrial sewage of a large amount of high-concentration hardly-degradables, serious harm is caused to environment.Traditional biochemical method process is adopted to be difficult to meet technology and economic requirement to this kind of waste water.The efficient treatment technology of development high density, poisonous, harmful organic industrial sewage, just seems increasingly urgent and very important.
In current water, the treatment technology of Persistent organic pollutants mainly contains: physical technique (as coprecipitation method, absorption method and extraction process etc.) and chemical technology (as Ozonation, burning method, Wet Catalytic Oxidation Method, photocatalytic method etc.).Though wherein physical method is simple to operate, running expense is low, because of thoroughly can not widespread use in the industry to the process of organic waste water.Chemical oxidation techniques is then applicable to the process of all kinds of organic waste water.The method such as ozone oxidation, photochemical catalytic oxidation is mainly applicable to the lower organic removal of concentration; Though burning method effectively can process high concentrated organic wastewater, but the method energy expenditure is comparatively large, only in COD value higher than industrially just economically feasible when 300g/L.By contrast, the Wet Oxidation Process grown up the 1950's is a kind of effective means processing high density, poisonous, harmful, bio-refractory organic waste water, is used widely.
For reducing temperature of reaction, reducing the reaction times, reduce facility investment and day-to-day operation expense, people have developed catalytic wet air oxidation on the basis that traditional wet is oxidized.The core of this kind of method is selecting of catalyzer and oxygenant.In catalyzer, can be divided into metal and non-metallic catalyst, metal catalyst comprises again precious metal and base metal.Although precious metal has active and stability preferably in wet oxidation process, expensive, investment cost is high.In non-precious metal catalyst, homogeneous transition metal ion, as the feature that soluble copper salt reaction conditions is gentle, catalytic efficiency is high, selectivity is good, is therefore applied in industrialization, but it reclaims or removes more difficult.Therefore, research and develop inexpensive, efficient, the key issue of Wet Oxidation Process promoted beyond doubt by the homogeneous catalyst easily reclaiming or remove.In non-metallic catalyst, carbon material receives increasing concern due to the characterization of adsorption of its uniqueness, chemical stability and thermostability, but the catalytic oxidation effect of carbon material and the effect of homogeneous transition metal ionic association need further research.On oxygenant, although oxygen is conventional oxygenant, traditional working method passes into air or oxygen in reactor, and device is complicated, troublesome poeration.Hydrogen peroxide is also paid close attention to by people in recent years because oxidation capacity is strong, easy to use.Current hydrogen peroxide is mainly used in the oxidation under low-temperature atmosphere-pressure condition, and the research carrying out wet oxidation is at high temperature under high pressure less.Therefore, with homogeneous phase base metal ion and carbon material for catalyzer, with hydrogen peroxide as oxidant, the technology of carrying out wet oxidation at high temperature under high pressure will be improve a new way of wet oxidation effect.
Summary of the invention
For the problem of catalyzer and processing condition in current high concentration hard-degraded organic waste water Wet Oxidation Process, the object of the invention is to find the Catalytic Wet Oxidation technology that a kind of working cost is low, easy to operate, organic removal rate is high.It is characterized in that in a kettle., add waste water, first regulate wastewater pH, add divalent iron salt again and carbon material is catalyzer, add hydrogen peroxide as oxidant, sealed by reactor, react certain hour after with vigorous stirring system temperature being progressively warming up to design temperature, water outlet pH value alkali is adjusted to neutrality.The pH value of reaction system is 2.5 ~ 3.5, hydrogen peroxide dosage is 1:20 ~ 1:2 with the ratio of raw wastewater COD, the ratio of carbon material and hydrogen peroxide dosage is 1:200 ~ 1:40, the ratio of divalent iron salt and hydrogen peroxide dosage is 1:2000 ~ 1:20, stirring velocity is 100 ~ 150r/min, the top temperature heated that progressively heats up is 160 ~ 240 DEG C, and the reaction times is 0.5 ~ 3h.
The object of the present invention is achieved like this: under acidic conditions, and divalent iron salt and hydrogen peroxide Fenton occur and react, and discharges .OH by an oxidation operation part in waste water; When the temperature to 150 DEG C of reaction system, hydrogen peroxide starts to decompose, and produce oxygen, reaction system pressure is raised, the existence of oxygen partial pressure not only maintains the operation of " wet type " condition, also for reaction provides oxygenant.Jointly do in waste water, free radical reaction to occur under the condition of oxygenant at the katalysis of divalent iron salt and carbon material and hydrogen peroxide and oxygen, generate the free radical that oxidation capacity is stronger, promote organic degraded in waste water.After reaction terminates, the pH value of process water outlet is transferred to neutrality, and iron gets off with the form flocculation sediment of oxyhydroxide, promotes being separated of iron and carbon material and water, can be removed the organism in water simultaneously by flocculation adsorption effect further.
Relative to existing method, outstanding advantages of the present invention makes catalyzer with ferrous iron, hydrogen peroxide as oxidant in (1) reaction system, adopts the heating that progressively heats up, Fenton oxidation and wet oxidation are combined, improves organic oxidation efficiency; (2) in wet oxidation system, do not need outer oxygen, by hydrogen peroxide decompose themselves, produce oxygen to system pressurization, easy to operate, operational process is simple; (3) divalent iron salt used in reaction system and carbon material inexpensive, efficient, be easy to get, reaction terminates easily to be separated from system afterwards.
Specific implementation method
Embodiment 1: in 200mL reactor, adds 100mL printing wastewater, uses H 2sO 4with NaOH, the pH value of waste water is adjusted to 3.5, adds the hydrogen peroxide 6mL of 30% respectively, powder activated carbon 50mg and FeSO 450mg, seals reactor, and low whipping speed is that under 100r/min condition, heating makes temperature of reaction system progressively rise to 240 DEG C, and the reaction times is 2.0h, with NaOH, the pH value of system is adjusted to 7.0 after naturally cooling to room temperature, measures COD and TOC of supernatant liquor.Test-results shows, when temperature of reaction is 150 DEG C, system starts pressurization, and its maximum pressure is 1.6MPa, by this treating processes, the COD of waste water is down to 4491mg/L from 34702mg/L, and clearance reaches 87.06%, TOC is down to 104.3mg/L from 10600mg/L, and clearance reaches 99.01%
Embodiment 2: in 200mL reactor, adds 100mL dyeing waste water, uses H 2sO 4with NaOH, the pH value of waste water is adjusted to 3.0, adds the hydrogen peroxide 6mL of 30% respectively, powder activated carbon 10mg and FeSO 450mg, sealed by reactor, low whipping speed is adopt progressively temperature-raising method that system temperature is heated to 190 DEG C under 120r/min condition, and the reaction times is 1.0h, with NaOH, the pH value of system is adjusted to 6.5 after naturally cooling to room temperature, measures COD and TOC of supernatant liquor.Test-results shows, when temperature of reaction is 150 DEG C, system starts pressurization, and its maximum pressure is 1.2MPa, by this treating processes, the COD of waste water is down to 668.2mg/L from 9227.1mg/L, and clearance reaches 92.76%, TOC is down to 321.7mg/L from 1867.2mg/L, and clearance reaches 82.78%
Embodiment 3: in 400mL reactor, adds 200mL dyeing waste water, uses H 2sO 4with NaOH, the pH value of waste water is adjusted to 2.5, adds the hydrogen peroxide 10mL of 30% respectively, powder activated carbon 20mg and FeSO 4120mg, sealed by reactor, low whipping speed is adopt progressively temperature-raising method that system temperature is heated to 160 DEG C under 150r/min condition, and the reaction times is 3.0h, with NaOH, the pH value of system is adjusted to 6.8 after naturally cooling to room temperature, measures COD and TOC of supernatant liquor.Test-results shows, when temperature of reaction is 150 DEG C, system starts pressurization, and its maximum pressure is 1.4MPa, by this treating processes, the COD of waste water is down to 93.3mg/L from 4613.4mg/L, and clearance reaches 97.98%, TOC is down to 249.7mg/L from 1248.5mg/L, and clearance reaches 80%.

Claims (1)

1. one kind processes the method for high concentration hard-degraded organic waste water, it is characterized in that in a kettle., add waste water, first regulate wastewater pH, add divalent iron salt again and carbon material is catalyzer, add hydrogen peroxide as oxidant, reactor is sealed, after with vigorous stirring system temperature being progressively warming up to design temperature, reacts certain hour; Water outlet pH value alkali is adjusted to neutrality, the pH value of reaction system is 2.5 ~ 3.5, hydrogen peroxide dosage is 1:20 ~ 1:2 with the ratio of raw wastewater COD, the ratio of carbon material and hydrogen peroxide dosage is 1:200 ~ 1:40, the ratio of divalent iron salt and hydrogen peroxide dosage is 1:2000 ~ 1:20, stirring velocity is 100 ~ 150r/min, and the top temperature of the heating that progressively heats up is 160 ~ 240 DEG C, and the reaction times is 0.5 ~ 3h.
CN201310287290.8A 2013-07-10 2013-07-10 A kind of method processing high concentration hard-degraded organic waste water Expired - Fee Related CN103332774B (en)

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CN103708646B (en) * 2013-12-16 2015-10-28 中国天辰工程有限公司 A kind of Caprolactam industrial waste water treatment method
CN105330047A (en) * 2014-05-26 2016-02-17 中国石油化工股份有限公司 Method for processing high-concentration dibutyl phthalate-containing organic waste water
CN107552052B (en) * 2017-10-25 2020-01-31 四川师范大学 Treatment method of refractory organic wastewater
CN109231625A (en) * 2018-09-07 2019-01-18 薛芳 A kind of high temperature oxidation process method and apparatus of organic wastewater

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Patent Citations (8)

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Publication number Priority date Publication date Assignee Title
TW524779B (en) * 1998-05-01 2003-03-21 Ind Tech Res Inst Process for chemically oxidizing wastewater with reduced sludge production
JP2003245678A (en) * 2002-02-26 2003-09-02 Mitsubishi Gas Chem Co Inc Waste liquid treatment method by catalyst
JP2004066219A (en) * 2002-06-10 2004-03-04 Mitsubishi Electric Corp Water treatment system and water treatment method
JP2004074088A (en) * 2002-08-21 2004-03-11 Mitsubishi Gas Chem Co Inc Treatment method for waste liquid containing chemical polishing liquid
JP2006075773A (en) * 2004-09-10 2006-03-23 Mitsubishi Gas Chem Co Inc Purification method of soil ground water polluted by hardly decomposable organic compound
JP2009045508A (en) * 2007-08-13 2009-03-05 Mitsubishi Gas Chem Co Inc Method for treating waste water in epoxy resin production
CN101993162A (en) * 2009-08-27 2011-03-30 中国石油化工股份有限公司 Method for treating reverse osmosis concentrated water
CN102198989A (en) * 2011-04-22 2011-09-28 安徽国星生物化学有限公司 Method for treating PMIDA wastewater

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